Bradley Nursery School in Nelson was closed on Monday as a mark of respect following the death of headteacher Miss Claire Lucas, who was killed alongside her partner Mark in the accident on A59 at Broughton, near Skipton.
The driver of the Mercedes van involved in the collision with the couple's Nissan Juke was arrested at the scene and has now been released under investigation while inquiries continue.
The couple lived in West Craven.
Sue Nike, chairman of governors at Bradley Nursery School, said: "It is with the deepest sadness that we can confirm that our headteacher Claire Lucas, and her partner Mark, both lost their lives in a road accident on Friday.
"Claire will be greatly missed. She was such a well-loved and inspirational headteacher. We have closed the school as a mark of respect for Claire, and also to help us all to try to come to terms with this.
"Our overriding priority is to provide support to pupils and colleagues, and we are working with Lancashire County Council to make sure that additional care and help is in place.
"All our thoughts and prayers are with her family and friends at this very sad time."
Pendle MP Andrew Stephenson also paid tribute to "inspirational" headteacher Claire.
Mr Stephenson said: "I’m shocked and saddened to hear that Claire Lucas tragically died in a car accident over the weekend.
"Claire was very well known in Pendle, being the headteacher of the outstanding Bradley Nursery School in Nelson. She was an inspiration and a well-respected member of our community.
"This is a very tragic loss, which I know will be felt by many. I offer my deepest condolences to Claire’s friends and family, as well as to her colleagues, pupils and parents at Bradley Nursery."
North Yorkshire Police have appealed for witnesses to the accident to come forward with information.
Emergency services were called at around 9-40pm on Friday following reports of a two vehicle RTC. The collision involved a silver Mercedes Vito van and a white Nissan Juke.
Claire and Mark were the two occupants of the Nissan Juke.
A woman from the Mercedes van was taken to hospital with serious injuries.
Police are appealing for any witnesses who may have seen either of the vehicles prior to the collision, or were on the A59 at the time and may have dashcam footage, to contact North Yorkshire Police.
Anyone with information is asked to call 101 quoting reference number 12200013851. Alternatively you can email [email protected]